US4454146A - Synergistic preservative compositions - Google Patents

Synergistic preservative compositions Download PDF

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Publication number
US4454146A
US4454146A US06/378,372 US37837282A US4454146A US 4454146 A US4454146 A US 4454146A US 37837282 A US37837282 A US 37837282A US 4454146 A US4454146 A US 4454146A
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United States
Prior art keywords
component
bacteria
preservative
methyl
isothiazolin
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/378,372
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English (en)
Inventor
Gayle E. Borovian
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lever Brothers Co
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Lever Brothers Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Assigned to LEVER BROTHERS COMPANY reassignment LEVER BROTHERS COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BOROVIAN, GAYLE E.
Priority to US06/378,372 priority Critical patent/US4454146A/en
Priority to DE8383200671T priority patent/DE3360877D1/de
Priority to AT83200671T priority patent/ATE15749T1/de
Priority to EP83200671A priority patent/EP0094721B1/de
Priority to US06/576,286 priority patent/US4499071A/en
Publication of US4454146A publication Critical patent/US4454146A/en
Application granted granted Critical
Priority to US06/666,023 priority patent/US4540570A/en
Priority to US06/717,737 priority patent/US4555400A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention is directed to preservatives, compositions containing preservatives, and methods for inhibiting the growth of microorganisms.
  • compositions are susceptible to contamination by microorganisms such as bacteria.
  • Such compositions include, but are by no means limited to, personal care products such as shampoos, cosmetics, and soaps and household products such as laundry detergents, hard surface cleaners, fabric softeners and the like.
  • preservatives are frequently added to the formula.
  • the contaminating microorganisms are, however, adaptable and, with time, often become immune to the preservative. Therefore, there is a continuing need for new preservatives which will inhibit the growth of microorganisms.
  • an object of the present invention to provide a new preservative, compositions containing the new preservative, and methods for inhibiting the growth of microorganisms.
  • a further object of this invention is to provide a preservative comprising two components which inhibit the growth of microorganisms synergistically in the presence of each other.
  • a first component selected from the group consisting of benzoic acid, formaldehyde, a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one in a ratio of about 5:1 to 1:5, benzisothiazalone, and mixtures thereof;
  • a second component having the following formula: ##STR3## wherein x is about 2 to 33 and r is H or CH 3 and mixtures thereof; wherein said second component is present in an amount at which said second component acts synergistically with said first component to kill or inhibit the growth of microorganisms.
  • the present invention provides a composition suitable for use as a personal care product or a household product, said composition being susceptible to contamination by microorganisms, comprising a preservative in an amount sufficient to kill or to inhibit the growth of said microorganisms wherein said preservative comprises:
  • a first component selected from the group consisting of benzoic acid, formaldehyde, a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one in a ratio of about 5:1 to 1:5, benzisothiazalone, and mixtures thereof;
  • a second component having the following formula: ##STR4## and mixtures thereof; wherein said second component is present in an amount which acts synergistically with said first component to kill or inhibit the growth of microorganisms.
  • the present invention provides a method for killing or inhibiting the growth of microorganisms comprising contacting said microorganisms with a biocidal or biostatic amount of a compound having the formula: ##STR5## wherein x is about 2 to 33 and R represents hydrogen or methyl, or ##STR6##
  • the present invention provides a method for killing or inhibiting the growth of microorganisms comprising contacting said microorganisms with a preservative comprising:
  • a first component selected from the group consisting of benzoic acid, formaldehyde, a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one in a ratio of about 5:1 to 1:5, benzisothiazalone, and mixtures thereof;
  • a second component selected from the group of compounds having the following formula: ##STR7## and mixtures thereof; wherein said second component is present in an amount at which said second component acts synergistically with said first component to kill or inhibit the growth of microorganisms.
  • the present invention provides a preservative comprising:
  • a first component selected from the group consisting of a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one in a ratio of about 5:1 to 1:5, benzisothiazalone, and mixtures thereof;
  • the present invention provides a composition suitable for use as a personal care product or a household product, said composition beiing susceptible to contamination by microorganisms, comprising a preservative in an amount sufficient to kill or inhibit the growth of said microorganisms wherein said preservative comprises:
  • the present invention provides a method for killing or inhibiting the growth of microorganisms comprising contacting said microorganisms with a preservative comprising a first component selected from the group consisting of a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one in a ratio of about 5:1 to 1:5, benzisothiazalone, and mixtures thereof and a second component having the formula: ##STR10## wherein said second component is present in an amount at which said second component acts synergistically with said first component to kill or inhibit the growth of microorganisms.
  • the present invention relates to a preservative.
  • Preservatives are chemical components which either kill or inhibit the growth of microorganisms and, in particular, bacteria.
  • Preservatives which kill microorganisms are said to be biocidal while those that inhibit the growth of microorganisms are said to be biostatic.
  • the bacteria of particular interest in the present invention are gram negative bacteria and, more particularly, those of the genus Pseudomonas.
  • the preservatives presently claimed are especially effective against Pseudomonas cepacia.
  • the preservatives of the present invention comprise at least two components, herein called the first component and the second component.
  • the first component comprises one or more traditional preservatives.
  • Some suitable traditional preservatives include benzoic acid, sorbic acid, formaldehyde, gluteraldehyde, benzisothiazalone (A), and a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one (B) and 2-methyl-4-isothiazolin-3-one (C) in a ratio of about 5:1 to 1:5, preferably 3 to 1.
  • Compounds A, B and C have the following structures: ##STR11##
  • Compounds B and C in a ratio of about 3:1 are sold by Rohm and Haas under the trade names Kathon CG.
  • Compound A is sold by ICI under the trade name Proxel.
  • the second component of the present invention comprises at least one compound which, in combination with the first component, kills or inhibits the microorganisms discussed above synergistically.
  • the second component may or may not be biocidal or biostatic when used by itself.
  • the first compound is biocidal or biostatic at lower concentrations than in the absence of the second compound.
  • Suitable second compounds include dyes having the following formulas: ##STR12## wherein x is about 2 to 33, preferably about 5 to 33 and most preferably about 16 to 33 and R represents hydrogen or methyl, preferably methyl. This formula will be referred to as I in this application; and ##STR13##
  • This compound will be referred to as II in this application.
  • the preferred second compound is I wherein x is about 33 and R is methyl.
  • the compounds having Formula I are blue dyes described in U.S. Pat. No. 4,137,243 to Farmer and assigned to the Milliken Research Corporation. These compounds may be prepared by treating quinizarin in water with sodium hydroxide and sodium hydrosulfite. The resulting leucoquinizarin is treated with two moles of a polyoxyethylenediamine or a polyoxypropylenediamine. The later diamines are available from the Jefferson Chemical Company under the trade name Jeffamine. The resulting product is oxidized with air. The conditions for these reactions are described in the Farmer patent in Example 2, which is incorporated herein by reference.
  • mesidine II may be prepared by condensing one mole of 1,4-dichloroanthraquinone with 2 moles of mesidine sulfonate and converting the resulting product to the sodium salt.
  • the structure of mesidine is 2,4,6-trimethyl-3-aminobenzenesulfonate.
  • the amount of the second compound in the preservative composition is that amount which interacts synergistically with the first compound to kill or inhibit the growth of microorganisms.
  • the weight ratio of the second compound to the first compound will be 1000:1 to 1:10, preferably 100:1 to 1:5, and most preferably 10:1 to 1:1.
  • the preservatives are present in compositions which are susceptible to degradation due to microorganisms.
  • suitable compositions include any composition in which preservatives may safely be used.
  • Some suitable compositions include personal care products and household products.
  • Some suitable personal care products include shampoos, hair conditioners, skin creams, suntan lotions and soaps.
  • Some suitable household products include laundry detergents, dishwashing detergents, hard surface cleaners and fabric softeners.
  • the amount of the preservative in the composition is that amount which effectively inhibits the growth of the contaminating microorganism.
  • the actual amount depends upon numerous factors. For example, one factor is the length of time the composition is to be stored. The longer the storage period, the higher the concentration of preservative.
  • the concentration of the preservative is a function of the particular first component and second component combination used, of the particular microorganism to be killed or inhibited, and the particular medium in which the microorganism is growing, as well as other variables.
  • the total preservative will be present in the composition in amounts from about 0.02 to 1% by weight, preferably 0.05 to 0.5% by weight and most preferably 0.075 to 0.125% by weight.
  • a third embodiment of the present invention is a method for killing or inhibiting the growth of microorganisms. It has been discovered that the second components described above unexpectedly inhibit the growth of the microorganisms described above. It is desirable, of course, to add one of the first components to the second component in order to take advantage of the synergistic effect.
  • the preferred second component is I.
  • the preferred synergistic combination is I and a mixture of B and C in a ratio of about 3 to 1.
  • the present invention is operative at any pH. Where benzoic acid is used, the pH must be less than 7, preferably less than 5.5 and most preferably less than 4 to ensure that dissociation of the benzoic acid does not occur.
  • the Gradient Plate procedure was used to determine preservative activity as measured in "Minimum Inhibitory Concentration" (MIC) values. This method was described by Janet C. Curry in the 1965 CSMA Proceedings, 52nd Annual meeting.
  • a square phage-type petrie dish was prepared so as to contain a base layer of acidified TSA (Difco's Tryptic Soy Ager, adjusted to pH 4 with citric acid) hardened in the form of a wedge.
  • a top layer of acidified TSA containing a specific level of preservative component was hardened with the plate in a level position. A test agent in the top layer diffuses into the base layer causing a concentration gradient on the surface.
  • Preservatives were prepared having gradient plate dilutions ranging from 1,000 to 0.5 ppm of the first component and from 1,500 to 500 ppm of the second component.
  • This example compares the activity of formaldehyde and benzoic acid toward Pseudomonas Cepacia grown in the formulas described in Comparatives Examples A, B and C as well as that described in Example 1.
  • the method is that described in Example 2.
  • the results are shown in Table 2.
  • Formaldehyde exhibited an MIC of about 30 ppm on the inocula from the unpreserved Comparative Example A.
  • the bacteria used in this example appears to be weaker than those used in Examples 3 to 5.
  • the synergism between compounds I and II on the one hand and benzoic acid and a mixture of B and C on the other is apparent.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US06/378,372 1982-05-14 1982-05-14 Synergistic preservative compositions Expired - Lifetime US4454146A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US06/378,372 US4454146A (en) 1982-05-14 1982-05-14 Synergistic preservative compositions
DE8383200671T DE3360877D1 (en) 1982-05-14 1983-05-10 Synergistic preservative compositions, products containing them and processes for using them
AT83200671T ATE15749T1 (de) 1982-05-14 1983-05-10 Synergistische konservierungszusammensetzungen, diese enthaltende produkte und verfahren zu ihren gebrauch.
EP83200671A EP0094721B1 (de) 1982-05-14 1983-05-10 Synergistische Konservierungszusammensetzungen, diese enthaltende Produkte und Verfahren zu ihren Gebrauch
US06/576,286 US4499071A (en) 1982-05-14 1984-02-02 Synergistic preservative compositions
US06/666,023 US4540570A (en) 1982-05-14 1984-10-29 Synergistic preservative compositions
US06/717,737 US4555400A (en) 1982-05-14 1985-03-28 Synergistic preservative compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US06/378,372 US4454146A (en) 1982-05-14 1982-05-14 Synergistic preservative compositions

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US06/576,286 Division US4499071A (en) 1982-05-14 1984-02-02 Synergistic preservative compositions

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EP (1) EP0094721B1 (de)
AT (1) ATE15749T1 (de)
DE (1) DE3360877D1 (de)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4851139A (en) * 1987-08-26 1989-07-25 The Clorox Company Isotropic fabric softener composition containing fabric mildewstat
US5023267A (en) * 1987-02-25 1991-06-11 W. R. Grace & Co.-Conn. Microbiological control agent
US5028620A (en) * 1988-09-15 1991-07-02 Rohm And Haas Company Biocide composition
US5308858A (en) * 1991-12-05 1994-05-03 Electric Power Research Institute Use of additives for preservative carrier oils to improve their efficacy against wood decay
US5648348A (en) * 1991-10-28 1997-07-15 Mona Industries, Inc. Phospholipid antimicrobial compositions
US5750402A (en) * 1995-06-02 1998-05-12 Plant Cell Technology, Inc. Compositions and methods to prevent microbial contamination of plant tissue culture media
US20040151742A1 (en) * 2001-05-09 2004-08-05 Wolfgang Beilfuss Alcohol-free liquid concentrate for preserving cosmetics, household and technical products
WO2006032397A1 (en) * 2004-09-23 2006-03-30 Unilever Plc Laundry treatment compositions
US20060106024A1 (en) * 2004-11-16 2006-05-18 Richard Levy Microbicidal composition
US20080096789A1 (en) * 2004-09-23 2008-04-24 Batchelor Stephen N Laundry Treatment Composition
US20090044846A1 (en) * 2004-10-20 2009-02-19 Bsh Bosch Und Siemens Hausgeraete Gmbh Lighting device for a water-bearing domestic appliance
US20090223003A1 (en) * 2004-09-23 2009-09-10 Stephen Norman Batchelor Laundry treatment compositions
US20090286709A1 (en) * 2007-01-19 2009-11-19 Eugene Steven Sadlowski Novel whitening agents for cellulosic substrates
US9856439B2 (en) 2010-11-12 2018-01-02 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
CN112608055A (zh) * 2020-10-23 2021-04-06 科之杰新材料集团福建有限公司 防腐剂组合物及其制备方法和应用

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1272001A (en) * 1985-03-04 1990-07-31 John A. Jakubowski Synergistic admixtures containing 2-bromo-2- bromomethylglutaronitrile
US4822511A (en) * 1988-05-06 1989-04-18 Rohm And Haas Company Preservative compositions comprising a synergistic mixture of isothiagolones
CA2080121C (en) * 1990-04-18 2001-11-20 Albert Gordon Anderson Anthraquinones as inhibitors of sulfide production from sulfate-reducing bacteria
EP0570794A3 (en) * 1992-05-18 1994-06-15 Givaudan Roure Int Preservative systems
GB0314211D0 (en) * 2003-06-18 2003-07-23 Unilever Plc Laundry treatment compositions
EP1772055A1 (de) * 2005-10-04 2007-04-11 Rohm and Haas France SAS Synergistische Mikrobizidzusammensetzungen enthaltend N-Alkyl-1,2-benzoisothiazolin-3-on
CN107488358B (zh) * 2016-06-13 2019-05-28 南京工业大学 一类羊毛低温染色用酸性染料及其制备方法
CN107488359B (zh) * 2016-06-13 2019-10-29 南京工业大学 一类含聚醚胺链段蓝色酸性染料及其制备方法
CN116529346A (zh) * 2020-11-10 2023-08-01 特洛伊技术第二股份有限公司 具有明显改进活性的bit组合物

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US2121928A (en) * 1934-03-21 1938-06-28 Firm Chemical Works Anthraquinone dyestuffs and process for their manufacture
US3065123A (en) * 1959-06-24 1962-11-20 Ici Ltd Process for control of micro-organisms
US3761488A (en) * 1967-03-09 1973-09-25 Rohm & Haas 3-isothiazolones
US3947594A (en) * 1973-05-07 1976-03-30 Gaf Corporation 4-Halo-1-hydroxyanthraquinone containing fungicidal composition
US3958928A (en) * 1975-05-05 1976-05-25 Lever Brothers Company Reduced-staining colorant system for liquid laundry detergents
US4137243A (en) * 1976-08-24 1979-01-30 Milliken Research Corporation Polymeric anthraquinone derived colorants
US4144024A (en) * 1978-02-21 1979-03-13 Lever Brothers Company Reduced-staining colorant system
US4252694A (en) * 1967-03-09 1981-02-24 Rohm And Haas Company Cleaning composition containing 3-isothiazolones

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US2121928A (en) * 1934-03-21 1938-06-28 Firm Chemical Works Anthraquinone dyestuffs and process for their manufacture
US3065123A (en) * 1959-06-24 1962-11-20 Ici Ltd Process for control of micro-organisms
US3761488A (en) * 1967-03-09 1973-09-25 Rohm & Haas 3-isothiazolones
US4105431A (en) * 1967-03-09 1978-08-08 Rohm And Haas Company 3-Isothiazolones as biocides
US4252694A (en) * 1967-03-09 1981-02-24 Rohm And Haas Company Cleaning composition containing 3-isothiazolones
US3947594A (en) * 1973-05-07 1976-03-30 Gaf Corporation 4-Halo-1-hydroxyanthraquinone containing fungicidal composition
US3958928A (en) * 1975-05-05 1976-05-25 Lever Brothers Company Reduced-staining colorant system for liquid laundry detergents
US4110238A (en) * 1975-05-05 1978-08-29 Lever Brothers Company Reduced-staining colorant system
US4137243A (en) * 1976-08-24 1979-01-30 Milliken Research Corporation Polymeric anthraquinone derived colorants
US4144024A (en) * 1978-02-21 1979-03-13 Lever Brothers Company Reduced-staining colorant system

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5023267A (en) * 1987-02-25 1991-06-11 W. R. Grace & Co.-Conn. Microbiological control agent
US4851139A (en) * 1987-08-26 1989-07-25 The Clorox Company Isotropic fabric softener composition containing fabric mildewstat
US5028620A (en) * 1988-09-15 1991-07-02 Rohm And Haas Company Biocide composition
US5648348A (en) * 1991-10-28 1997-07-15 Mona Industries, Inc. Phospholipid antimicrobial compositions
US5650402A (en) * 1991-10-28 1997-07-22 Mona Industries, Inc. Phospholipid antimicrobial compositions
US5308858A (en) * 1991-12-05 1994-05-03 Electric Power Research Institute Use of additives for preservative carrier oils to improve their efficacy against wood decay
US5750402A (en) * 1995-06-02 1998-05-12 Plant Cell Technology, Inc. Compositions and methods to prevent microbial contamination of plant tissue culture media
US20040151742A1 (en) * 2001-05-09 2004-08-05 Wolfgang Beilfuss Alcohol-free liquid concentrate for preserving cosmetics, household and technical products
EP2009088A3 (de) * 2004-09-23 2009-01-14 Unilever PLC Zusammensetzungen zur Wäschebehandlung
US8268016B2 (en) 2004-09-23 2012-09-18 The Sun Products Corporation Laundry treatment compositions
US20080096789A1 (en) * 2004-09-23 2008-04-24 Batchelor Stephen N Laundry Treatment Composition
WO2006032397A1 (en) * 2004-09-23 2006-03-30 Unilever Plc Laundry treatment compositions
US20090223003A1 (en) * 2004-09-23 2009-09-10 Stephen Norman Batchelor Laundry treatment compositions
US8715369B2 (en) 2004-09-23 2014-05-06 The Sun Products Corporation Laundry treatment compositions
EP2133409A3 (de) * 2004-09-23 2010-03-03 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Zusammensetzungen zur Wäschebehandlung
US20090044846A1 (en) * 2004-10-20 2009-02-19 Bsh Bosch Und Siemens Hausgeraete Gmbh Lighting device for a water-bearing domestic appliance
EP1665933A3 (de) * 2004-11-16 2006-08-16 Rohm and Haas Company Mikrobizide Zusammensetzung
EP1820398A1 (de) * 2004-11-16 2007-08-22 Rohm and Haas Company Mikrobizide Zusammensetzung
US7468384B2 (en) 2004-11-16 2008-12-23 Rohm And Haas Company Microbicidal composition
US20060106024A1 (en) * 2004-11-16 2006-05-18 Richard Levy Microbicidal composition
US8247364B2 (en) 2007-01-19 2012-08-21 The Procter & Gamble Company Whitening agents for cellulosic substrates
US8367598B2 (en) 2007-01-19 2013-02-05 The Procter & Gamble Company Whitening agents for cellulosic subtrates
US8703688B2 (en) 2007-01-19 2014-04-22 The Procter & Gamble Company Whitening agents for cellulosic substrates
US20090286709A1 (en) * 2007-01-19 2009-11-19 Eugene Steven Sadlowski Novel whitening agents for cellulosic substrates
US10526566B2 (en) 2007-01-19 2020-01-07 The Procter & Gamble Company Whitening agents for cellulosic substrates
US11198838B2 (en) 2007-01-19 2021-12-14 The Procter & Gamble Company Whitening agents for cellulosic substrates
US11946025B2 (en) 2007-01-19 2024-04-02 The Procter & Gamble Company Whitening agents for cellulosic substrates
US9856439B2 (en) 2010-11-12 2018-01-02 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US10435651B2 (en) 2010-11-12 2019-10-08 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US10655091B2 (en) 2010-11-12 2020-05-19 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
CN112608055A (zh) * 2020-10-23 2021-04-06 科之杰新材料集团福建有限公司 防腐剂组合物及其制备方法和应用

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DE3360877D1 (en) 1985-10-31
EP0094721A1 (de) 1983-11-23
ATE15749T1 (de) 1985-10-15
EP0094721B1 (de) 1985-09-25

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